CN106701083B - A kind of II type quantum dot fluorescence material of manganese ion doping and its preparation method and application - Google Patents
A kind of II type quantum dot fluorescence material of manganese ion doping and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of II type quantum dot fluorescence material of manganese ion doping and its preparation method and application, the fluorescent material is to be doped into Mn in the core A of II type quantum dot A/B2+II type quantum dot A:Mn/B of manganese ion doping is formed, then coats the broad stopband ZnS shell of high quality to get manganese ion doping II type quantum dot (A:Mn/B/ZnS) fluorescent material.Compared with the existing technology, the present invention in II type quantum dot by introducing the divalent manganesetion Mn of doping2+As energy terminal and exciton coupler, overcome II type exciton (oscillator strength is low) easily by the weakness of defect capture, to improve the luminous efficiency of II type exciton.
Description
Technical field
The invention discloses a kind of II type quantum dot fluorescence materials of manganese ion doping and its preparation method and application, belong to glimmering
Luminescent material technical field.
Background technique
The important feature of II type semiconductor-quantum-point first is that the electrons and holes of II type exciton with preferable space point
From oscillator strength is weak, and rate of irradiation is smaller, is easy to be influenced by non-radiative defect, to have lower fluorescent quantum
Efficiency.High temperature nucleating growth and prolonged annealing can be played the role of reducing defect, and II type exciton of Lai Tigao shines,
But it is inefficient.
Summary of the invention
Goal of the invention: in view of the above technical problems, the present invention provides a kind of II type quantum dot fluorescence materials of manganese ion doping
Material and its preparation method and application.
Technical solution: the present invention provides a kind of II type quantum dot fluorescence materials of manganese ion doping, in II type quantum dot AB
In be doped into Mn2+II type quantum dot A:Mn/B of manganese ion doping is formed, then coats the broad stopband ZnS shell of high quality to get institute
State II type quantum dot fluorescence material of manganese ion doping.
Preferably, the II type quantum dot A/B is CdS/ZnSe, ZnSe/CdS, ZnTe/ZnSe or ZnSe/ZnTe
Deng, it is made of the different materials that two kinds of band structures are staggered, after excitation, electronics is in a kind of lower material of conduction band,
Hole is in the higher another material of valence band；Such as: 1.A CdS, B ZnSe, electronics is in CdS layer after excitation, and hole is in
ZnSe layer；2.A is ZeTe, B ZnSe, and electronics is in ZnSe layer after excitation, and hole is in ZnTe layers.
As another preferred embodiment, the II type quantum dot fluorescence material introduces Mn in the inner nuclear layer far from surface2+Doping
As the energy terminal and coupler of II type exciton.
The present invention also provides the preparation methods of the II type quantum dot fluorescence material of manganese ion doping, including following step
It is rapid:
(1) preparation nucleation doped semiconductor quantum dot A:Mn: nucleus MnS is prepared using manganese stearate and excessive S, then is wrapped
A Shell Materials are covered, doped quantum dot A:Mn is prepared, purification gained quantum dot simultaneously dissolves, the nucleus as next step shell cladding；
(2) the B shell and ZnS shell of high quality are coated: utilizing the precursor solution containing shell element, it is fast using high temperature
The B shell and ZnS shell of fast method for coating cladding high quality, obtain the solution containing A:Mn/B/ZnS quantum dot；
(3) A:Mn/B/ZnS quantum dot made from purification step (2) is to get the fluorescent material.
Preferably, first coating one layer of ZnS transition zone in the step (1) before coating A Shell Materials, being conducive to
The diffusion of Mn.
As another preferred embodiment, the step (2) in cladding high quality B shell and ZnS shell, method for coating include with
Lower step: heating the precursor solution containing B shell, and nucleus obtained by injection step (1) is then injected into certain B shell
Another precursor solution, formed A:Mn/B, annealing；The precursor solution of ZnS is reinjected, forms ZnS shell, and anneal, i.e.,
Obtain the solution containing A:Mn/B/ZnS quantum dot.
Fluorescent material of the present invention is preferably doped into Mn in II type Quantum dots CdS/ZnSe2+Form manganese ion doping II
Type Quantum dots CdS: then Mn/ZnSe coats the broad stopband ZnS shell of high quality again, is formed by fluorescent material, preparation side
Method the following steps are included:
(1) it prepares doped semiconductor Quantum dots CdS: Mn: being prepared into manganese sulfide nano grain using manganese stearate and excess S powder
Son, then certain thickness CdS (centre can introduce a ZnS thin layer as transition zone) is coated, certain time of annealing finally purifies molten
Solution is in a small amount of octadecylene ODE solvent, to be prepared into doped quantum dot CdS:Mn；
(2) prepare doped semiconductor Quantum dots CdS: Mn coats ZnSe/ZnS shell: the quantum that will be prepared in step (1)
In the precursor solution of point injection Zn, Se precursor solution is slowly injected at 300 DEG C, anneals about 5 minutes, is warming up to 320 DEG C, then
Annealing about 5 minutes；Then S precursor solution is slowly injected, is annealed about ten minutes, so that CdS:Mn/ZnSe/ZnS be prepared
Quantum dot；
(3) purify the Quantum dots CdS for preparing: Mn/ZnSe/ZnS, be dissolved in n-hexane or toluene to get.
The present invention finally also discloses the application of the II type quantum dot fluorescence material of manganese ion doping, the fluorescent material
For making biological fluorescent labelling and solar battery etc..
Divalent manganesetion Mn2+The quantum dot of doping would generally issue bright yellow emission, and Stokes is displaced (absorption peak
Between fluorescence peak) it is larger, due to spin forbidden, Mn2+Fluorescence lifetime is longer, therebetween Mn2+Actually play energy accumulator
Effect.For the quantum dot that a type shines, usually there is lesser Stokes displacement, it is same what is be excited to be difficult to realize manganese
When, almost all return passes to a type exciton to energy again.And quantum dot and Mn that II type is luminous2+With preferable excitation and energy
Amount returns to the matching of transmitting.Due to Mn2+Exciton can be inhibited well by non-radiative defect capture.Mn2+Be used as energy
Terminal can convey more excitons to luminous zone, furthermore when luminous, Mn2+Coupling with exciton can further subtract
The non-radiative capture of few exciton, to improve quantum efficiency.
In the present invention, first passage manganese metal is entrained in introducing divalent manganesetion Mn in II type quantum dot2+As energy
Terminal and exciton coupler, reduce capture of the exciton by defect, to improve II type excitonic luminescence of quantum dot.Nucleus
Quality, shell quality and adulterate manganese ion position, may all influence to a certain extent manganese ion as energy terminal with
The effect of coupler.The position for improving nucleus and shell quality and optimization doping manganese ion, can further obtain brighter
II type exciton emission.It is essential that the meaning for introducing doping manganese ion is, the case where adulterating manganese ion position optimization
Under, the defects of quantum dot can be insensitive to and the easily prepared quantum dot for obtaining that there is relatively bright II type exciton emission.
The electrons and holes in II type exciton in II type quantum dot have preferable separation: its luminescent lifetime in space
It is long, it can be used for fluorescent marker；For realizing Laser emission, its threshold value is low；It is easy to dissociate into free carrier, can be applicable to
In the preparation of solar battery.And the introducing of manganese ion is adulterated, the influence of defect is reduced, new mechanism is introduced, is improved
The function of II type quantum dot.It is expected to further push the research and application of metal-doped II type quantum dot.
The Mn that the present invention is embodied2+Doped quantum dot CdS:Mn/ZnSe/ZnS, the quantum efficiency of II type excitonic luminescence
It significantly improves (up to 60% or more), fluorescence lifetime is obviously prolonged.
Technical effect: compared with the existing technology, the present invention in II type quantum dot by introducing the divalent manganesetion of doping
Mn2+As energy terminal and exciton coupler, overcome II type exciton (oscillator strength is low) easily by the weakness of defect capture, thus
Improve the luminous efficiency of II type exciton.
Detailed description of the invention
Fig. 1 is photo of undoped and additive Mn the CdS/ZnSe/ZnS quantum dot solution under ultraviolet light irradiation.
Fig. 2 is the absorption spectrum and fluorescence Spectra of gained additive Mn CdS:Mn/ZnSe/ZnS semiconductor-quantum-point: dotted line is to inhale
Spectrum is received, solid line is fluorescence Spectra.
Fig. 3 is the schematic diagram that the present invention designs: doping manganese ion Mn2+Energy terminal and coupling as II type exciton
Device reduces II type exciton to the sensitivity of defect, improves its quantum efficiency.
Specific embodiment
With reference to the accompanying drawing and specific example, the present invention is furture elucidated, it should be understood that these examples are merely to illustrate this hair
Bright rather than limit the scope of the invention, after the present invention has been read, those skilled in the art are to of the invention various etc.
The modification of valence form falls within the application range as defined in the appended claims.
Embodiment 1
One kind mixing manganese Quantum dots CdS: the specific synthesis step of Mn/ZnSe/ZnS:
(1) it prepares the nucleation doped semiconductor Quantum dots CdS of high quality: Mn: in an argon atmosphere, utilizing manganese stearate
0.03g and excessive S powder 0.045g is prepared into nucleus MnS in 260 DEG C of reactions in 12ml octadecene solution, and first injection is a small amount of
0.06g zinc stearate coats the diffusion that one layer of transition zone is conducive to manganese, anneals 10-20 minutes at 280 DEG C, then on 230 DEG C of left sides
The cadmium stearate of right injection 0.25-0.5g or so coats thicker CdS Shell Materials, anneals about 15-30 minutes；Purification institute
It obtains quantum dot and is dissolved in the nucleus that a small amount of octadecylene is coated as next step shell；
(2) prepare doped semiconductor Quantum dots CdS: Mn coats ZnSe/ZnS shell: in an argon atmosphere, by Zn presoma
ZnO (2.5mmol), oleic acid OA (12.5mmol) and tri-n-octylphosphine oxide TOPO (4g) are stirred under certain temperature (~100 DEG C)
Mix degasification certain time (~1 hour)；~350 DEG C of setting is heated to milky white solution bleach；Temperature is down to~320 DEG C of injections
Quantum dot (~80nmol) solution sets 300 DEG C, and injecting the Se precursor solution of 0.5mmol, (Se powder is dissolved in tri-n-octyl phosphine
TOP, is made into the solution of 2mol/L, is diluted to 0.5mol/L using octadecylene), it grows 5 minutes；~320 DEG C are set again, are moved back
Fire 5 minutes；Finally injecting the S precursor solution of a certain amount of (1~3.5mmol), (S powder is dissolved in tri-n-octyl phosphine TOP, is made into
The solution of 2mol/L is diluted to 1mol/L using octadecylene), it anneals 10-20 minutes, wherein extracting certain sample.
(3) purify the Quantum dots CdS prepared: Mn/ZnSe/ZnS is dissolved in toluene or n-hexane.
Quantum dot solution after being purified as obtained by the preparation of embodiment one, the luminous situation under ultraviolet light irradiation, such as Fig. 1
Shown in (right side), there is apparent enhancing than the undoped II type quantum dot light emitting of similar approach synthesis；Its corresponding absorption fluorescence light
Spectrogram is as shown in Fig. 2, wherein low energy absorbs (less than the forbidden bandwidth of each component material) wider range, from two kinds of materials
Between absorption (transition of the electronics from the higher material of valence band to another lower material of conduction band), wherein fluorescence spectrum compared with
Narrow (being less than 40nm), is II type excitonic luminescence, rather than from the transmitting with divalent manganesetion；The schematic diagram of relevant design such as Fig. 3
It is shown.
Embodiment 2
According to 1 method of embodiment, prepare slightly smaller size core (diameter~3.5nm) mixes manganese Quantum dots CdS: Mn/ZnSe/
ZnS fluorescent material.
Gained fluorescent material is detected according to the detection method of embodiment 1, as a result can be obtained, II type luminous peak position blue shift,
It has apparent enhancing than the undoped II type quantum dot light emitting of similar approach synthesis.
Embodiment 3
According to 1 method of embodiment, prepare slightly larger size core (diameter~4.5nm) mixes manganese Quantum dots CdS: Mn/ZnSe/
ZnS fluorescent material.
Gained fluorescent material is detected according to the detection method of embodiment 1, as a result can be obtained, II type luminous peak position red shift,
It has apparent enhancing than the undoped II type quantum dot light emitting of similar approach synthesis.
Embodiment 4
According to 1 method of embodiment, prepares super thick (~12 ZnSe molecular layers thicks 1) ZnSe shell and mix manganese quantum dot
CdS:Mn/ZnSe/ZnS fluorescent material.
Gained fluorescent material is detected according to the detection method of embodiment 1, as a result can be obtained, II type luminous peak position red shift,
It has apparent enhancing than the undoped II type quantum dot light emitting of similar approach synthesis.
The application of 5 fluorescent material of embodiment
By 1 gained fluorescent material of embodiment, the quantum dot of water phase, gained bioluminescence are made by the method that ligand is converted
The fluorescence of marker material is relatively strong and has the advantage of longer life.
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of II type quantum dot fluorescence material of manganese ion doping, which is characterized in that be doped into Mn in II type quantum dot A/B2+
II type quantum dot A:Mn/B of manganese ion doping is formed, then coats the broad stopband ZnS shell of high quality to get the manganese ion doping
II type quantum dot (A:Mn/B/ZnS) fluorescent material；
The preparation method of the II type quantum dot fluorescence material of manganese ion doping, comprising the following steps:
(1) preparation nucleation doped semiconductor quantum dot A:Mn: nucleus MnS is prepared using manganese stearate and excessive S, then coats A
Shell Materials prepare doped quantum dot A:Mn, and purification gained quantum dot simultaneously dissolves, the nucleus as next step shell cladding；
(2) the B shell and ZnS shell of high quality are coated: the precursor solution containing shell element is utilized, using high temperature Fast Packet
Coating method coats the B shell and ZnS shell of high quality, obtains the solution containing A:Mn/B/ZnS quantum dot；
(3) A:Mn/B/ZnS quantum dot made from purification step (2) is to get the fluorescent material.
2. II type quantum dot fluorescence material of manganese ion doping according to claim 1, which is characterized in that the II type quantum
Point A/B is CdS/ZnSe, ZnSe/CdS, ZnTe/ZnSe or ZnSe/ZnTe.
3. II type quantum dot fluorescence material of manganese ion doping according to claim 1, which is characterized in that the II type quantum
Point fluorescent material introduces Mn in the nucleus far from surface2+It adulterates as the energy of II type exciton produced by II type quantum dot of excitation
Measure terminal and coupler.
4. the preparation method of any one of the claim 1-3 II type quantum dot fluorescence material of manganese ion doping, which is characterized in that
The following steps are included:
(1) preparation nucleation doped semiconductor quantum dot A:Mn: nucleus MnS is prepared using manganese stearate and excessive S, then coats A
Shell Materials prepare doped quantum dot A:Mn, and purification gained quantum dot simultaneously dissolves, the nucleus as next step shell cladding；
(2) the B shell and ZnS shell of high quality are coated: the precursor solution containing shell element is utilized, using high temperature Fast Packet
Coating method coats the B shell and ZnS shell of high quality, obtains the solution containing A:Mn/B/ZnS quantum dot；
(3) A:Mn/B/ZnS quantum dot made from purification step (2) is to get the fluorescent material.
5. the preparation method of II type quantum dot fluorescence material of manganese ion doping according to claim 4, which is characterized in that institute
It states in step (1), one layer of ZnS transition zone for being conducive to manganese ion diffusion is first coated before coating A Shell Materials.
6. the preparation method of II type quantum dot fluorescence material of manganese ion doping according to claim 4, which is characterized in that institute
The B shell and ZnS shell of cladding high quality in step (2) are stated, method for coating is the following steps are included: before one containing B shell
Liquid solution heating is driven, nucleus obtained by injection step (1) is then injected into another precursor solution of certain B shell, forms A:
Mn/B, annealing；The precursor solution of ZnS is reinjected, forms ZnS shell, and anneal to get A:Mn/B/ZnS quantum dot is contained
Solution.
7. the application of any one of the claim 1-3 II type quantum dot fluorescence material of manganese ion doping, which is characterized in that described
Fluorescent material is used for biological fluorescent labelling or solar battery.
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